CN101111783B - Substrate with antireflection coating - Google Patents
Substrate with antireflection coating Download PDFInfo
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- CN101111783B CN101111783B CN2006800033827A CN200680003382A CN101111783B CN 101111783 B CN101111783 B CN 101111783B CN 2006800033827 A CN2006800033827 A CN 2006800033827A CN 200680003382 A CN200680003382 A CN 200680003382A CN 101111783 B CN101111783 B CN 101111783B
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
Abstract
To provide a substrate with an antireflection film having a high visible light transmittance, a low reflectance and a high film resistivity, and having no cracking even when subjected to heat treatment. A substrate with an antireflection film comprising a transparent substrate and an antireflection film having even number layers in total of a coating film made of a high refractive material having a refractive index of at least 1.90 and a coating film made of a low refractive material having a refractive index of at most 1.56 laminated in this order from the transparent substrate side, wherein at least one coating film made of a high refractive material is a single layer film (a) of a titanium oxynitride layer, a laminated film (b) containing a titanium oxide layer and a zirconium oxide layer or a laminated film (c) containing a titanium oxynitride layer and a zirconium oxide layer.
Description
Technical field
The present invention relates to matrix with antireflection film.
Background technology
The windscreen of automobile (windshield) is hoped low etc. to visible light transmittance height, reflectivity.As the antireflection film of the low-reflection glass that satisfies this characteristic, used the stacked film of titanium nitride layer and silicon oxide layer.In addition, in recent years, consider in that the window cover is on glass to fix up an aerial wire, except above-mentioned characteristic, also wish not shielding electromagnetic wave.
But the stacked film of titanium nitride layer and silicon oxide layer therefore can shielding electromagnetic wave because the film resistance rate is low.
Relative therewith, as to visible light transmittance height, reflectivity is low, the film resistance rate is high antireflection film, known stacked film by titanium oxide layer and silicon oxide layer.
But the stacked film with titanium oxide layer and silicon oxide layer has in bending machining or reinforcement as the glass plate of antireflection film and adds man-hour, because the problem of crackle appears in thermal treatment on this stacked film.
Summary of the invention
Therefore, have visible light transmittance height, reflectivity is low, the antireflection film of crackle also can not appear in film resistance rate height through thermal treatment matrix even the object of the present invention is to provide.
The inventor is in order to finish above-mentioned purpose, and the stacked film of titanium oxide layer and silicon oxide layer has been carried out conscientious research, and titanium oxide layer carries out crystallization and shrinks and cause when found that the appearance crackle of this stacked film through thermal treatment the time owing to thermal treatment.
The inventor further carries out conscientious research, found that by making titanium oxide layer contain the method for nitrogen, perhaps with titanium oxide layer in abutting connection with the method for zirconia layer is set, perhaps with the method for these and usefulness, thereby even can reach through thermal treatment crackle does not appear yet.So finished the present invention.
That is, main idea of the present invention is as follows.
The matrix of band antireflection film, it is to have transparent base, and will by refractive index the formed tunicle of the high-index material more than 1.90 and by refractive index the formed tunicle of the low-index material below 1.56 from above-mentioned transparent base side begin according to this sequential cascade even level and the matrix of band antireflection film of antireflection film, it is characterized in that at least 1 layer of the tunicle that is formed by above-mentioned high-index material is the monofilm (a) of titanium oxynitrides layer, contain the stacked film (b) of titanium oxide layer and zirconia layer or contain the stacked film (c) of titanium oxynitrides layer and zirconia layer.
The matrix of band antireflection film, it is to have transparent base, and will by refractive index the formed tunicle of the high-index material more than 1.90 and by refractive index the formed tunicle of the low-index material below 1.56 from above-mentioned transparent base side begin according to this sequential cascade even level and the matrix of band antireflection film of antireflection film, it is characterized in that at least 1 layer of the tunicle that is formed by above-mentioned high-index material is the monofilm (a) of titanium oxynitrides layer, the stacked film (c1) of the stacked film of titanium oxide layer and zirconia layer (b1) or titanium oxynitrides layer and zirconia layer.
Matrix as above-mentioned [2] described band antireflection film is characterized in that, at least 1 layer of the tunicle that is formed by above-mentioned high-index material is the stacked film (c1) of titanium oxynitrides layer and zirconia layer.
The matrix of band antireflection film, it is to have transparent base, and the tunicle that will form in the high-index material more than 1.90 by refractive index and the tunicle that forms at the low-index material below 1.56 by refractive index from above-mentioned transparent base side begin according to 4 layers of this sequential cascades the matrix of band antireflection film of antireflection film, it is characterized in that above-mentioned antireflection film is to begin to be laminated with in order the tunicle that is formed in the high-index material more than 1.90 by refractive index from the transparent base side, the monofilm of monox, the stacked film of titanium oxynitrides layer and zirconia layer (c1), the antireflection film of the monofilm of monox.
Matrix as [4] described band antireflection film is characterized in that, the tunicle that is formed in the high-index material more than 1.90 by above-mentioned refractive index is the monofilm of titanium oxide layer.
Matrix as each described band antireflection film in above-mentioned [1]～[5] is characterized in that, is pressed the albedometer of visible light by the reflection of above-mentioned antireflection face below 6% with 60 ° of light from the incident of above-mentioned antireflection film side of incident angle.
Matrix as each described band antireflection film in above-mentioned [1]～[6] is characterized in that, the nitrogen amount with respect to titanium in the above-mentioned titanium oxynitrides layer is 0.1～80at%.
Matrix as each described band antireflection film in above-mentioned [1]～[7] is characterized in that, the nitrogen amount with respect to titanium in the preceding above-mentioned titanium oxynitrides layer of thermal treatment is 2～40at%.
Matrix as each described band antireflection film in above-mentioned [1]～[8] is characterized in that, after the thermal treatment in the above-mentioned titanium oxynitrides layer nitrogen amount with respect to titanium be 0.1～20at%.
The job operation of the matrix of band antireflection film, it is characterized in that, have the matrix of each described band antireflection film in above-mentioned [1]～[9] is sent into the heating process that is heated to the bending forming temperature in the heating furnace, and bending forming is the operation of desirable shape.
Even the matrix of band antireflection film of the present invention is low to visible light transmittance height, reflectivity, film resistance rate height crackle can not occur through thermal treatment yet in antireflection film.
Embodiment
Below, explain the present invention.
The matrix of band antireflection film of the present invention is to have transparent base is arranged, and the tunicle that will form in the high-index material more than 1.90 by refractive index and the tunicle that forms at the low-index material 1.56 below by refractive index from above-mentioned transparent base side begin according to this sequential cascade even level and must the matrix of band antireflection film of antireflection film, wherein, at least 1 layer of the tunicle that is formed by above-mentioned high-index material is the monofilm (a) of titanium oxynitrides layer, contain the stacked film (b) of titanium oxide layer and zirconia layer or contain the stacked film (c) of titanium oxynitrides layer and zirconia layer.Preferably, the matrix of band antireflection film of the present invention is for having transparent base, and the tunicle that will form in the high-index material more than 1.90 by refractive index and the tunicle that forms at the low-index material below 1.56 by refractive index from above-mentioned transparent base side begin according to this sequential cascade even level and the matrix of band antireflection film of antireflection film, wherein, at least 1 layer of the tunicle that is formed by above-mentioned high-index material is the monofilm (a) of titanium oxynitrides layer, the stacked film (c1) of the stacked film of titanium oxide layer and zirconia layer (b1) or titanium oxynitrides layer and zirconia layer.
The matrix of band antireflection film of the present invention preferably in 60 ° of incident angles from the light of antireflection film side incident by the reflection of antireflection face by visible reflectance below 6%.As then antireflection property is abundant in above-mentioned scope.
The transparent base that uses among the present invention is not limited to water white material, in transmissivity is not damaged the scope of purpose of the present invention, also can use coloured material.Special preferred glass.
There is no particular limitation for glass, for example transparent or painted float glass (glass that is made by float glass process), makes it painted infrared absorbing glass.In addition, also can use tempered glass.The concrete infrared absorbing glass that contains coloring components such as iron particle in the soda-lime glass that preferably makes.
The matrix of band antireflection film of the present invention also can with other arbitrarily substrate in combination use.For example, can form and will use the matrix of the band antireflection film of the present invention that glass plate makes as transparent base, clip with another glass plate intermediate coat such as polyvinyl butyral stacked and compound glass use.This compound glass is suitable as the windshield of automobile.
The matrix of band reflectance coating of the present invention on above-mentioned transparent base, have the tunicle that forms in the high-index material more than 1.90 by refractive index and the tunicle that forms at the low-index material 1.56 below by refractive index from the transparent base side begin according to this sequential cascade even level and must antireflection film.
Among the present invention, high-index material is represented refractive index at the material more than 1.90, and low-index material is meant that refractive index is at the material below 1.56.
The stacked tunicle that forms by high-index material and preferably add up to 2 layers, 4 layers, 6 layers or 8 layers by the tunicle that low-index material forms, more preferably 2 layers, 4 layers or 6 layers, preferred especially 4 layers.
At least 1 layer of the tunicle that forms by high-index material be the titanium oxynitrides layer monofilm (a), contain the stacked film (b) of titanium oxide layer and zirconia layer or contain the stacked film (c) of titanium oxynitrides layer and zirconia layer.Like this, contain nitrogen in the titanium oxide layer, or zirconia layer is set, can prevent that the crackle when thermal treatment from occurring with the titanium oxide layer adjacency by making.Below, each film of above-mentioned (a)～(c) is described.
The monofilm of＜titanium oxynitrides layer (a) 〉
The monofilm of titanium oxynitrides layer (a) is only by titanium oxynitrides (TiO
xN
y) layer film that forms.The titanium oxynitrides layer is compared with titanium oxide layer, is difficult to carry out crystallization during thermal treatment.Therefore can suppress the appearance of crackle.
Titanium oxynitrides (TiO
xN
y) layer is 0.1～80at% with respect to the nitrogen amount of titanium preferably.As in above-mentioned scope, it is outstanding then to suppress the effect that crackle occurs with respect to the nitrogen amount of titanium.In order to suppress the more remarkable effect that crackle occurs, the nitrogen amount with respect to titanium before the thermal treatment is 2～40at%, is preferably 3～40at% especially.
In addition, better for optical characteristics such as reflectivity, transmissivities, the nitrogen amount with respect to titanium after the thermal treatment is preferably 0.1～20at%, is preferably 0.1～10at% especially, especially preferred 0.1～5at%.
In addition, in the present invention, the composition of titanium oxynitrides layer (with respect to the nitrogen amount of titanium) can wait and analyze by x-ray photoelectron spectroscopy (XPS), ESCA.
The ratio of oxygen and nitrogen in the titanium oxynitrides layer (being specially the value of x and y) is difficult to direct mensuration.But can roughly get 1.8～2.1 value with respect to the nitrogen amount of titanium and value that it is generally acknowledged (x+y) by what try to achieve, infer its value roughly by mensuration.For example, as in the scope of 0.1at%, the value of y fixedly the time, then can be released x=1.799～2.099, y=0.001 with respect to the nitrogen amount of titanium.
As example, the value of x and y in the preferred composition of above-mentioned titanium oxynitrides layer is shown in table 1.This value has been put down in writing the value of the value of y being fixed and calculating based on prerequisite same as described above.
[table 1]
| Nitrogen amount (at%) with respect to titanium | X | y |
| 0.1 | 1.799～2.099 | 0.001 |
| 2 | 1.78～2.08 | 0.02 |
| 3 | 1.77～2.07 | 0.03 |
| 5 | 1.75～2.05 | 0.05 |
| 10 | 1.70～2.00 | 0.10 |
| 40 | 1.40～1.70 | 0.40 |
| 80 | 1.00～1.30 | 0.80 |
Thermal treatment can be adopted common bending machining or strengthen the condition that adopts in the processing and carry out, can be in 550～700 ℃ temperature range, carry out in preferred 600～700 ℃ temperature range.Concrete example is as carrying out under 650 ℃ of design temperatures, 15 minutes condition of heat treatment time.
The geometric thickness of titanium oxynitrides layer is preferably 5～160nm, more preferably 40～140nm.As the then anti-reflection effect of antireflection film increase in above-mentioned scope, and be not easy to occur crackle, and can reduce the set-back of matrix.In addition, because the reflected colour of the reflected colour of the matrix of band antireflection film and transparent base is roughly the same, so the geometric thickness of titanium oxynitrides layer is preferably 80～120nm especially.
For the manufacture method of titanium oxynitrides layer as described later.
＜contain the stacked film (b) of titanium oxide layer and zirconia layer 〉
The stacked film (b) that contains titanium oxide layer and zirconia layer is to contain the titanium oxide layer more than 1 layer and the stacked film of the zirconia layer more than 1 layer.The titanium oxide layer that contains in the stacked film (b) is preferably 1 layer or 2 layers, and the zirconia layer that contains in the stacked film (b) is preferably 1 layer or 2 layers.In addition, titanium oxide layer that preferably contains in the stacked film (b) and zirconia layer are in abutting connection with stacked.
Zirconia layer is most of monocline crystallization when film forming.In addition, the lattice of zirconia layer and titanium oxide layer size is an equal extent, carries out lattice matched easily.Therefore, by in abutting connection with such zirconia layer, arrange again at the internal crystal framework of titanium oxide layer in the time of can suppressing thermal treatment and carry out crystallization, thereby the contraction when being not easy to cause thermal treatment.Also think to have to a certain degree structure arranged by titanium oxide layer when the film forming, thereby be difficult to cause the arrangement again (that is, being difficult to crystallization) of titanium dioxide in addition.Therefore, can suppress titanium oxide layer and crackle occur.
The structure of stacked film (b) can exemplify following structure so long as just there is no particular limitation in abutting connection with stacked with titanium oxide layer and zirconia layer.
The stacked film of titanium oxide layer and zirconia layer (b1),
The stacked film of titanium oxide layer, zirconia layer, titanium oxide layer,
The stacked film of zirconia layer, titanium oxide layer, zirconia layer,
The stacked film of titanium oxide layer, zirconia layer, titanium oxide layer, zirconia layer.
Wherein, preferred stacked film (b1), stacked film (b1) is with titanium dioxide (TiO
2) and zirconia (ZrO
2) the stacked film of layer adjacency.Stacked film (b1) just can suppress the generation of crackle with the less number of plies, and is therefore good economically, useful in the practicality.
More specifically can exemplify following structure.
Begin by ZrO from the transparent base side
2/ TiO
22 layers of structure that form,
Begin by TiO from the transparent base side
2/ ZrO
2/ TiO
23 layers of structure that form,
Begin by ZrO from the transparent base side
2/ TiO
2/ ZrO
23 layers of structure that form,
Begin by ZrO from the transparent base side
2/ TiO
2/ ZrO
2/ TiO
24 layers of structure that form.
Structure ([transparent base side] ZrO for example that has zirconia layer in the transparent base side of titanium oxide layer
2/ TiO
22 layers of structure of [face side]), has the structure of zirconia layer between 2 layers the titanium oxide layer (for example, by [transparent base side] ZrO
2/ TiO
2/ ZrO
2/ TiO
24 layers of structure that [face side] forms, by [transparent base side] TiO
2/ ZrO
2/ TiO
23 layers of structure that [face side] forms) consider preferred from the aspect of the appearance that suppresses crackle.
Other also preferably begins by ZrO from the transparent base side
2/ TiO
2/ ZrO
2/ TiO
24 layers of structure that form.As with the aggregate thickness of this 4 tunic integral thickness as the tunicle that forms by high-index material, to compare with 2 layers of structure that form by titanium oxide layer and zirconia layer, per 1 layer thickness of titanium oxide layer can be thinner, also can suppress the appearance of crackle thus.
Only otherwise influence characteristics such as reflectivity, transmissivity, film resistance value, in the scope of not damaging the object of the invention, also can have other layer that forms by high-index material in the stacked film (b).
Other layer that is formed by high-index material as stacked film (b) can have can use titanium oxide layer, zinc oxide film, tantalum oxide layers, zirconia layer, niobium oxide layer, silicon nitride layer, zirconium nitride layer, aln layer etc.
Preferred 40～the 160nm of geometric thickness of stacked film (b), more preferably 50～140nm.As in above-mentioned scope, then the anti-reflection effect of antireflection film increases, and the warpage that is not easy crackle to occur and can also reduces matrix.In addition, if the geometric thickness of stacked film (b) is then equal, therefore preferred especially with the reflected colour of the reflected colour of the matrix of antireflection film and transparent base at 80～130nm.
Stacked film (b) is by ZrO
2/ TiO
2During 2 layers of structure forming, titanium oxide layer is preferred 30～150nm in the scope of the geometric thickness that is no more than stacked film (b), preferred especially 70～120nm.
In addition, by TiO
2/ ZrO
2/ TiO
2The 3 layers of structure that forms and by ZrO
2/ TiO
2/ ZrO
2/ TiO
2During 4 layers of structure forming, each titanium oxide layer is preferably 10～80nm.In addition, if the geometric thickness of each titanium oxide layer is 30～60nm, then equal, therefore preferred especially with the reflected colour of the reflected colour of the matrix of antireflection film and transparent base.
Preferred 5～the 50nm of the geometric thickness of zirconia layer, preferred especially 10～40nm.
The geometric thickness of zirconia layer is when 5nm is above, and the crystallization part is more during film forming, can more effectively suppress the appearance of crackle in the titanium oxide layer.
The refractive index of zirconia layer is littler than the refractive index of titanium oxide layer.Therefore, the refractive index of stacked film (b) is littler than the monofilm of titanium oxide layer.The geometric thickness of zirconia layer is when 50nm is following, and the refractive index of stacked film (b) is fully high.
In addition, the geometric thickness of zirconia layer can effectively suppress zirconia layer self and have the possibility that occurs crackle than big stress when thermal treatment when 50nm is following.
Stacked film (b) can by titanium oxide layer, zirconia layer and as required be limited to getting of characteristics such as not influencing reflectivity, transmissivity, film resistance value by form folded layer by layer of other high-index material.Layer as being formed by this high refractive index layer can exemplify as titanium oxide layer, zinc oxide film, tantalum oxide layers, zirconia layer, niobium oxide layer, silicon nitride layer, zirconium nitride layer, aln layer etc.About the manufacture method of each layer as described later.
＜contain the stacked film (c) of titanium oxynitrides layer and zirconia layer 〉
The stacked film (c) that contains titanium oxynitrides layer and zirconia layer is to contain the titanium oxynitrides layer more than 1 layer and the stacked film of the zirconia layer more than 1 layer.The titanium oxynitrides layer that contains in the stacked film (c) is preferably 1 layer or 2 layers, and the zirconia layer that contains in the stacked film (c) is preferably 1 layer or 2 layers.In addition, preferably that the titanium oxynitrides layer and the zirconia layer adjacency that contain in the stacked film (c) is stacked.
Because stacked film (c) has the effect of above-mentioned monofilm (a) and the effect of stacked film (b) concurrently, therefore can more effectively suppress the appearance of crackle.
Titanium oxynitrides (the TiO of stacked film (c)
xN
y) layer in respect to the nitrogen amount of titanium and the titanium oxynitrides (TiO of above-mentioned (a)
xN
y) nitrogen amount with respect to titanium is identical in the monofilm of layer, and is also identical for the value of x and y.
The structure of stacked film (c) can be given an example as following structure so long as titanium oxynitrides layer and zirconia layer adjacency are stacked with regard to there is no particular limitation.
The stacked film of titanium oxynitrides layer and zirconia layer (c1),
The stacked film of titanium oxynitrides layer, zirconia layer, titanium oxynitrides layer,
The stacked film of zirconia layer, titanium oxynitrides layer, zirconia layer,
The stacked film of titanium oxynitrides layer, zirconia layer, titanium oxynitrides layer, zirconia layer.
Wherein preferred stacked film (c1).The stacked film of titanium oxynitrides layer and zirconia layer (c1) is titanium oxynitrides (TiO
xN
y) layer and zirconia (ZrO
2) the stacked film of layer adjacency.
More specifically preferred following structure.
Begin by ZrO from the transparent base side
2/ TiO
xN
yThe 2 layers of structure (c1-1) that form,
Begin by TiO from the transparent base side
xN
y/ ZrO
2/ TiO
xN
y3 layers of structure that form,
Begin by ZrO from the transparent base side
2/ TiO
xN
y/ ZrO
23 layers of structure that form,
Begin by ZrO from the transparent base side
2/ TiO
xN
y/ ZrO
2/ TiO
xN
y4 layers of structure that form.
Wherein, the transparent base side of titanium oxynitrides layer has structure ([transparent base side] ZrO for example of zirconia layer
2/ TiO
xN
y2 layers of structure of [face side]), has the structure of zirconia layer [for example by ZrO between 2 layers of titanium oxynitrides layer
2/ TiO
xN
y/ ZrO
2/ TiO
xN
y4 layers of structure that form]) preferred from the aspect that suppresses the crackle generation, preferred especially [transparent base side] ZrO
2/ TiO
xN
y2 layers of structure (stacked film (c1-1)) of [face side].
Preferred 40～the 160nm of geometric thickness of stacked film (c), more preferably 50～140nm.If in above-mentioned scope, then the anti-reflection effect of antireflection film increases, and is not easy to occur crackle, and can reduce the warpage of matrix.In addition, stacked film (c) if geometric thickness at 80～130nm, then the reflected colour with the matrix of antireflection film is identical with the reflected colour of transparent base, and is therefore preferred especially.
Stacked film (c) is by ZrO
2/ TiO
xN
yDuring 2 layers of structure forming, the thickness of titanium oxynitrides is preferably 30～150nm in the scope of the geometric thickness that is no more than stacked film (c), preferred especially 70～120nm.
In addition, for by TiO
xN
y/ ZrO
2/ TiO
xN
yThe 3 layers of structure that forms and by ZrO
2/ TiO
xN
y/ ZrO
2/ TiO
xN
yDuring 4 layers of structure forming, preferably each titanium oxynitrides layer is 10～80nm.In addition, when the geometric thickness of each titanium oxynitrides layer was 30～60nm, the reflected colour of the matrix of band antireflection film and the reflected colour of transparent base were equal, therefore preferred especially.
The geometric thickness of zirconia layer is preferably 5～50nm, more preferably 10～40nm.
The geometric thickness of zirconia layer is when 5nm is above, and the crystallization part is more during film forming, can more effectively suppress the appearance of crackle in the titanium oxynitrides layer.
The refractive index of zirconia layer is littler than the refractive index of titanium oxynitrides layer.Therefore, the refractive index of stacked film (c) is compared littler with the monofilm of titanium oxynitrides layer.If the geometric thickness of zirconia layer is below 50nm, the refractive index of stacked film (c) is fully high.
In addition, the geometric thickness of zirconia layer can suppress effectively that zirconia layer self has big stress and occurs the possibility of crackle during thermal treatment when 50nm is following.
In the stacked film (c1-1), TiO
xN
yThe geometric thickness of layer is preferably 70～120nm, preferred especially 90～110nm.ZrO
2The geometric thickness of layer is preferably 5～50nm.ZrO
2If the geometric thickness of layer is too small, then the abrasion performance of antireflection film descends sometimes, therefore is preferably 8～30nm especially.TiO
xN
yGeometric thickness and ZrO
2As long as the geometric thickness of layer satisfies above-mentioned scope, just can fully have anti-reflection effect and prevent that effect from appearring in crackle.Except these effects, for the warpage of the matrix of the time band antireflection film that is suppressed at thermal treatment, ZrO
2The geometric thickness and the TiO of layer
xN
yThe ratio of geometric thickness, when the geometric thickness of each layer satisfies in the above-mentioned scope, ZrO
2Layer/TiO
xN
yLayer is preferably 1/ (4～14).
In addition, stacked film (c) only otherwise influence characteristics such as reflectivity, transmissivity, film resistance value also can have other layer that is formed by high-index material in the scope of not damaging the object of the invention.Other layer as being formed by high-index material can exemplify as titanium oxide layer, zinc oxide film, tantalum oxide layers, zirconia layer, niobium oxide layer, silicon nitride layer, zirconium nitride layer, aln layer etc.Wherein preferred titanium oxide layer.
Can exemplify as by TiO as the structure of the stacked film with titanium oxide layer (c)
2/ ZrO
2/ TiO
xN
y3 layers of structure that form, by ZrO
2/ TiO
2/ ZrO
2/ TiO
xN
y4 layers of structure that form, by ZrO
2/ TiO
xN
y/ ZrO
2/ TiO
24 layers of structure that form.
For by TiO
2/ ZrO
2/ TiO
xN
yDuring 3 layers of structure forming, each titanium oxynitrides layer and titanium oxide layer are preferably 10～80nm.By ZrO
2/ TiO
2/ ZrO
2/ TiO
xN
yThe 4 layers of structure that forms and by ZrO
2/ TiO
xN
y/ ZrO
2/ TiO
2Each the titanium oxynitrides layer and the titanium oxide layer of 4 layers of structure that form are preferably 10～80nm.In addition, if the geometric thickness of each titanium oxynitrides layer and titanium oxide layer is 30～60nm, then the reflected colour with the matrix of antireflection film is identical with the reflected colour of transparent base, and is therefore good especially.
In addition, as described later for the manufacture method of each layer.
Among the present invention, as the tunicle that forms by high-index material, be preferably the stacked film (c) that contains titanium oxynitrides layer and zirconia layer in above-mentioned (a)～(c), particularly preferably the stacked film of titanium oxynitrides layer and zirconia layer (c1) especially preferably begins by ZrO from the matrix side
2Layer/TiO
xN
y2 layers of structure (c1-1) that layer forms.
Among the present invention, at least 1 layer of the tunicle that is formed by high-index material gets final product for any of above-mentioned (a)～(c).That is, when the tunicle that is formed by high-index material has more than 2 layers, also can have the layer outside above-mentioned (a)～(c).During this situation, being preferably from the transparent base tunicle that is formed by high-index material farthest is any of above-mentioned (a)～(c).
There is no particular limitation to the layer outside above-mentioned (a)～(c), can use known in the past layer.For example, titanium oxide layer, zinc oxide film, tantalum oxide layers, zirconia layer, niobium oxide layer, silicon nitride layer, zirconium nitride layer, aln layer.Wherein, preferred titanium oxide layer.
Among the present invention, because the total sum of the tunicle that is layered in the tunicle that is formed by high-index material on the matrix and is formed by low-index material is preferably 4 layers, therefore be preferably, the tunicle that is formed by high-index material that is equivalent to the 3rd layer is any of above-mentioned (a)～(c), be equivalent to the 1st layer high-index material layer for forms by above-mentioned known in the past high-index material layer.
The geometric thickness of above-mentioned (a)～(c) tunicle that is formed by high-index material in addition is preferably 5～200nm when this tunicle is titanium oxide layer, zinc oxide film, tantalum oxide layers, zirconia layer, niobium oxide layer, more preferably 5～100nm is preferably 5～60nm especially.In addition, this tunicle is preferably 5～160nm when being silicon nitride layer, zirconium nitride layer, aln layer, and more preferably 5～100nm is preferably 5～60nm especially.As in above-mentioned scope, then the anti-reflection effect of antireflection film increases, and is not easy to occur crackle, can also reduce the warpage of matrix.
The refractive index of the tunicle that is formed by high-index material is getting final product more than 1.90, preferably 2.00～2.60, more preferably 2.20～2.60.
There is no particular limitation to the tunicle that formed by low-index material, can use known in the past layer.
Preferred monox (SiO for example
2) layer.
The geometric thickness of the tunicle that is formed by low-index material is preferably 5～220nm, more preferably 20～140nm.If in above-mentioned scope, then anti-reflection effect increases, and is not easy to occur crackle, and can reduce the warpage of matrix.
The refractive index of the tunicle that is formed by low-index material is getting final product below 1.56, but preferably more than 1.45.
Among the present invention, the total sum of the tunicle that is formed by high-index material and the tunicle that is formed by low-index material is more than 4 layers the time, and the geometric thickness of the tunicle that is formed by high-index material of plural number existence can adopt equal thickness also difference can be arranged.This also is same for the tunicle that is formed by low-index material that plural number exists.
If the differentiated situation of geometric thickness of the tunicle that the example plural number exists, can for example add up to when ading up to 4 layers, the geometric thickness of the 1st layer the tunicle that is formed by high-index material is 5～20nm, the geometric thickness of the 2nd layer the tunicle that is formed by low-index material is 20～60nm, the geometric thickness of the 3rd layer the tunicle that is formed by high-index material is 70～130nm, and the geometric thickness of the 4th layer the tunicle that is formed by low-index material is 80～120nm.
The matrix of band antireflection film of the present invention can followingly obtain: on above-mentioned transparent base, will be by above-mentioned high-index material tunicle that forms and the tunicle that forms by above-mentioned low-index material, begin according to this sequential cascade even level from above-mentioned transparent base side, thereby form antireflection film.
The manufacture method of each layer below is described.
The layer that forms by high-index material for titanium oxynitrides layer, titanium oxide layer, zirconia layer and stacked as required other, and there is no particular limitation to constitute manufacture method by the layer of the formed tunicle of low-index material, can use known method in the past, all preferably come film forming by sputtering method.
Sputtering method can exemplify as dc sputtering, exchange sputtering method, high-frequency sputtering, magnetron sputtering system.Wherein, owing to process stabilizing, large tracts of land film forming, so preferred dc magnetron sputtering method easily, interchange magnetic tube sputtering method.
In the manufacturing of titanium oxynitrides layer, preference is as using TiO
x(1＜x＜2) as target, use the gas of the gas contain nitrogen atom to carry out the method for reactive sputtering method as sputter gas.
In the manufacturing of titanium oxide layer, preference is as using TiO
x(1＜x＜2) as target, use the gas of the gas contain oxygen atom to carry out the method for reactive sputtering method as sputter gas.
In the manufacturing of zirconia layer, preference as use zirconium as target, use the gas of the gas that contains oxygen atom to carry out the method for reactive sputtering method as sputter gas.
In the manufacturing of silicon oxide layer, preference as use silit (SiC) as target, use the gas of the gas that contains oxygen atom to carry out the method for reactive sputtering method as sputter gas.
In target, also can in the scope of not damaging feature of the present invention, mix known adulterants such as Al, Si, Zn.During this situation, the amount of adulterant preferably with respect to contained whole metallic atoms in the target below 20at%.
Contain the gas of nitrogen atom just there is no particular limitation as long as contain the gas of the gas of nitrogen atom, can exemplify gas, the gas of nitrogen atom and the mixed gas of inert gas as nitrogen atom.
The gas of nitrogen atom can exemplify as nitrogen (N
2), N
2O, NO, NO
2, NH
3
Can exemplify as rare gas such as helium, neon, argon gas, krypton gas, xenons as inert gas.Wherein, consider, be preferably argon gas from the easiness of economy and discharge.
They can use separately also and can use mixing more than 2 kinds.
Contain the gas of oxygen atom just there is no particular limitation as long as contain the gas of the gas of oxygen atom, can exemplify as the gas that contains oxygen atom, contain the gas of oxygen atom and the mixed gas of inert gas.
As the gas that contains oxygen atom, can exemplify as oxygen (O
2), carbon dioxide (CO
2).
For inert gas and above-mentioned same.
They can use separately also and can use mixing more than 2 kinds.
The condition of sputter can wait suitably according to kind, the thickness of the film of film forming to be determined.In addition, the general pressure of sputter gas is that the stable pressure that carries out glow discharge gets final product.
Below exemplify preferred implementation (1)～(4) of the matrix of band antireflection film of the present invention.Preferred implementation (1)～(3) wherein, special preferred implementation (2).Below, transparent base represents with G, and the tunicle that is formed by high-index material is as H, and the tunicle that is formed by low-index material is as L, and the lamination order that begins from the transparent base side separately is with the numeral of adding.
(1) G/H
1/ L
1Shown, have H
1For above-mentioned (a) and (b) or (c), by the transparent base of 2 layers of antireflection film that forms.
(2) G/H
1/ L
1/ H
2/ L
2Shown, have H
2For above-mentioned (a) and (b) or (c), by the transparent base of 4 layers of antireflection film that forms.
(3) G/H
1/ L
1/ H
2/ L
2/ H
3/ L
3Shown, have H
3For above-mentioned (a) and (b) or (c), by the transparent base of 6 layers of antireflection film that forms.
(4) G/H
1/ L
1/ H
2/ L
2/ H
3/ L
3/ H
4/ L
4Shown, have H
4For above-mentioned (a) and (b) or (c), by the transparent base of 8 layers of antireflection film that forms.
For embodiment (2), exemplify following preferred exemplary more specifically.ZrO (2-1)
2/ TiO
2/ ZrO
2/ TiO
2, the TiO in (2-2)
2/ ZrO
2/ TiO
2, the ZrO in (2-3)
2/ TiO
2, the ZrO in (2-4)
2/ TiO
xN
y, the TiO in (2-5)
xN
yBe equivalent to above-mentioned H
2
(2-1)G/TiO
2/SiO
2/ZrO
2/TiO
2/ZrO
2/TiO
2/SiO
2
(2-2)G/TiO
2/SiO
2/TiO
2/ZrO
2/TiO
2/SiO
2
(2-3)G/TiO
2/SiO
2/ZrO
2/TiO
2/SiO
2
(2-4)G/TiO
2/SiO
2/ZrO
2/TiO
xN
y/SiO
2
(2-5)G/TiO
2/SiO
2/TiO
xN
y/SiO
2
There is no particular limitation to the purposes of the matrix of band antireflection film of the present invention, can be used for purposes widely.Be suitable for the windscreen of automobile for example or deck sash, various display with glass, glass for building purposes, solar cell with cover glass etc., be particularly suitable for the windscreen of automobile.
The windscreen of automobile etc. has the article of curved surface can be by sending into the matrix of band antireflection film of the present invention in the heating furnace, is heated to the heating process of bending forming temperature and bends to the operation that forms desirable shape and obtain.Bending forming can carry out in the temperature range about 600～700 ℃ (being preferably 650～700 ℃).
Embodiment
Below exemplify embodiment the present invention is described.But the invention is not restricted to this.In the example shown below, example 1～14 is embodiment, and example 15 and example 16 are comparative example.
(manufacturing of the glass basis of band antireflection film)
Use infrared absorbing glass (サ Application ダ リ one Application, Asahi Glass corporate system, thickness 2mm, 2.3mm as glass basis.Hereinafter referred to as " VFL ") and colourless transparent glass (Asahi Glass corporate system, thickness 2.3mm.Hereinafter referred to as " FL "), form each layer thereon as described later, obtain having the glass basis of band antireflection film of the example 1～15 of formation shown below.
In addition, in the formation shown below, the formation of each layer is carried out in order from a left side.In addition, the geometric thickness of each layer is shown in the bracket.
For example, in example 1, the last formation of VFL TiO
2Layer is then at TiO
2Form SiO on the layer
2Layer is more then at SiO
2Form ZrO on the layer
2Layer is at ZrO
2Form TiO on the layer
2Layer is at TiO
2Form SiO on the layer
2Layer.Like this, on matrix, begin to form in order each layer from a left side.In addition, with VFL itself as example 16.
Example 1:VFL (2mm)/TiO
2(12nm)/SiO
2(41nm)/ZrO
2(20nm)/TiO
2(109nm)/SiO
2(111nm)
Example 2:VFL (2mm)/TiO
2(12nm)/SiO
2(41nm)/ZrO
2(15nm)/TiO
2(45nm)/ZrO
2(15nm)/TiO
2(40nm)/SiO
2(119nm)
Example 3:VFL (2mm)/TiO
2(12nm)/SiO
2(39nm)/TiO
2(45nm)/ZrO
2(20nm)/TiO
2(40nm)/SiO
2(94nm)
Example 4:VFL (2mm)/TiO
2(13nm)/SiO
2(44nm)/TiO
xN
y(120nm)/SiO
2(112nm)
Example 5:VFL (2mm)/TiO
2(10nm)/SiO
2(32nm)/ZrO
2(20nm)/TiO
xN
y(100nm)/SiO
2(107nm)
Example 6:VFL (2mm)/TiO
2(12nm)/SiO
2(39nm)/TiO
xN
y(113nm)/SiO
2(106nm)
Example 7:VFL (2mm)/TiO
2(11nm)/SiO
2(35nm)/ZrO
2(20nm)/TiO
xN
y(106nm)/SiO
2(108nm)
Example 8:VFL (2.3mm)/TiO
2(7.5nm)/SiO
2(30nm)/ZrO
2(10nm)/TiO
xN
y(97nm)/SiO
2(97nm)
Example 9:FL (2.3mm)/TiO
2(7nm)/SiO
2(29nm)/ZrO
2(19nm)/TiO
xN
y(103nm)/SiO
2(99nm)
Example 10:FL (2.3mm)/TiO
2(8nm)/SiO
2(32nm)/ZrO
2(16nm)/TiO
xN
y(98nm)/SiO
2(100nm)
Example 11:FL (2.3mm)/TiO
2(8nm)/SiO
2(32nm)/ZrO
2(30nm)/TiO
xN
y(98nm)/SiO
2(100nm)
Example 12:FL (2.3mm)/TiO
2(8nm)/SiO
2(32nm)/ZrO
2(8nm)/TiO
xN
y(98nm)/SiO
2(100nm)
Example 13:FL (2.3mm)/TiO
2(8nm)/SiO
2(32nm)/TiO
xN
y(98nm)/SiO
2(100nm)
Example 14:VFL (2.3mm)/TiO
2(8nm)/SiO
2(27nm)/ZrO
2(20nm)/TiO
xN
y(97nm)/SiO
2(91nm)
Example 15:VFL (2mm)/TiO
2(13nm)/SiO
2(43nm)/TiO
2(120nm)/SiO
2(112nm)
Example 16; VFL (2mm)
For example 1～7 and example 15 following each layers of formation.
＜TiO
2Layer 〉
In vacuum tank with TiO
x(1＜x＜2) target is arranged on the negative electrode as sputtering target, makes vacuum tank be vented to 1.3 * 10
-3Below the Pa.Then, import the mixed gas of argon gas 96sccm and oxygen 4sccm as sputter gas.At this moment, pressure becomes 5.7 * 10
-1Pa.Under this state, use the DC pulse power to carry out the reactive sputtering method, make on the handled object that is arranged in the vacuum tank and form TiO
2Layer.
＜SiO
2Layer 〉
In vacuum tank, the SiC target is arranged on the negative electrode as sputtering target, makes vacuum tank be vented to 1.3 * 10
-3Below the Pa.Then, import oxygen 100sccm as sputter gas.At this moment, pressure becomes 5.1 * 10
-1Pa.Under this state, use the DC pulse power to carry out the reactive sputtering method, make on the handled object that is arranged in the vacuum tank and form SiO
2Layer.
＜ZrO
2Layer 〉
In vacuum tank, the Zr target is arranged on the negative electrode as sputtering target, makes vacuum tank be vented to 1.3 * 10
-3Below the Pa.Then, import oxygen 60sccm as sputter gas.At this moment, pressure becomes 3.3 * 10
-1Pa.Under this state, use the DC pulse power to carry out the reactive sputtering method, make on the handled object that is arranged in the vacuum tank and form ZrO
2Layer.
＜TiO
xN
yLayer 〉
In vacuum tank with TiO
x(1＜x＜2) target is arranged on the negative electrode as sputtering target, makes vacuum tank be vented to 1.3 * 10
-3Below the pa.Then, import the mixed gas of argon gas and nitrogen as sputter gas.At this moment, pressure becomes 5.7 * 10
-1Pa.Under this state, use the DC pulse power to carry out the reactive sputtering method, make on the handled object that is arranged in the vacuum tank and form TiO
xN
yLayer.In addition,, use the mixed gas of argon gas 90sccm and nitrogen 10sccm,, use the mixed gas of argon gas 80sccm and nitrogen 20sccm as the sputter gas of example 6 and example 7 as the sputter gas in example 4 and the example 5.
For example 8～13, following each layer of formation.
＜TiO
2Layer 〉
In vacuum tank, the Ti target is arranged on the negative electrode as sputtering target, makes vacuum tank be vented to 2.7 * 10
-3Below the Pa.Then, become 4.0 * 10 with 50: 50 (mol ratio) importing argon gas and oxygen up to pressure as sputter gas
-1Pa.Under this state, use the DC pulse power to carry out the reactive sputtering method, make on the handled object that is arranged in the vacuum tank and form TiO
2Layer.
＜SiO
2Layer 〉
In vacuum tank, the polycrystalline Si target is arranged on the negative electrode as sputtering target, makes vacuum tank be vented to 2.7 * 10
-3Below the Pa.Then, the mixed gas [mixing ratio=60: 40 (mol ratio)] as sputter gas importing argon gas and oxygen becomes 4.0 * 10 up to pressure
-1Pa.Under this state, use AC power supplies to carry out the reactive sputtering method, make on the handled object that is arranged in the vacuum tank and form SiO
2Layer.
＜ZrO
2Layer 〉
In vacuum tank, the Zr target is arranged on the negative electrode as sputtering target, makes vacuum tank be vented to 2.7 * 10
-3Below the Pa.Then, the mixed gas [mixing ratio=70: 30 (mol ratio)] as sputter gas importing argon gas and oxygen becomes 6.7 * 10 up to pressure
-1Pa.Under this state, use the DC pulse power to carry out the reactive sputtering method, make on the handled object that is arranged in the vacuum tank and form ZrO
2Layer.
＜TiO
xN
yLayer 〉
In vacuum tank with TiO
x(1＜x＜2) target is arranged on the negative electrode as sputtering target, makes vacuum tank be vented to 2.7 * 10
-3Below the Pa.Then, import the mixed gas [mixing ratio=75: 10: 15 (mol ratio)] of argon gas, oxygen and nitrogen as sputter gas.At this moment, pressure becomes 6.7 * 10
-1Pa.Under this state, use the DC pulse power to carry out the reactive sputtering method, make on the handled object that is arranged in the vacuum tank and form TiO
xN
yLayer.
For example 14 following each layers of formation.
＜TiO
2Layer 〉
In vacuum tank with TiO
x(1＜x＜2) target is arranged on the negative electrode as sputtering target, makes vacuum tank be vented to 2.0 * 10
-3Below the Pa.Then, ratio importing argon gas and the oxygen with 93: 7 (mol ratio) becomes 4.3 * 10 as sputter gas up to pressure
-1Pa.Under this state, use AC power supplies to carry out the reactive sputtering method, make on the handled object that is arranged in the vacuum tank and form TiO
2Layer.
＜SiO
2Layer 〉
In vacuum tank, polycrystalline Si Al (Si:Al=90:10 (wt%)) target is arranged on the negative electrode as sputtering target, makes vacuum tank be vented to 2.0 * 10
-3Below the Pa.Then, the mixed gas [mixing ratio=52: 48 (mol ratio)] as sputter gas importing argon gas and oxygen becomes 4.3 * 10 up to pressure
-1Pa.Under this state, use AC power supplies to carry out the reactive sputtering method, make on the handled object that is arranged in the vacuum tank and form SiO
2Layer.
＜ZrO
2Layer 〉
In vacuum tank, the Zr target is arranged on the negative electrode as sputtering target, makes vacuum tank be vented to 2.0 * 10
-3Below the Pa.Then, [mixing ratio=70: 30 (mol ratio) becomes 3.0 * 10 up to pressure to import the mixed gas of argon gas and oxygen as sputter gas
-1Pa.Under this state, use the DC pulse power to carry out the reactive sputtering method, make on the handled object that is arranged in the vacuum tank and form ZrO
2Layer.
＜TiO
xN
yLayer 〉
In vacuum tank with TiO
x(1＜x＜2) target is arranged on the negative electrode as sputtering target, makes vacuum tank be vented to 2.0 * 10
-3Below the pa.Then, import the mixed gas [mixing ratio=93: 3.5: 3.5 (mol ratio)] of argon gas, oxygen and nitrogen as sputter gas.At this moment, pressure becomes 4.2 * 10
-1Pa.Under this state, use AC power supplies to carry out the reactive sputtering method, make on the handled object that is arranged in the vacuum tank and form TiO
xN
yLayer.
Below, the refractive index that constitutes the material of each layer is shown in table 2.Value when this value is wavelength 550nm.
[table 2]
| Example 1～7, example 15 | Example 8～14 | |
| TiO 2 | 2.49 | 2.43 |
| SiO 2 | 1.46 | 1.48 |
| ZrO 2 | 2.06 | 2.04 |
| TiO xN y | 2.44 | 2.39 |
(thermal treatment of the glass basis of band antireflection film)
The glass basis of the band antireflection film of the example 1～15 of above-mentioned gained and the VFL of example 16 are cut into 100nm * 100nm size respectively, heat-treat with small-sized band oven.Heat treated condition is 650 ℃ of design temperatures, heat-treated 15 minutes.
(proterties of the glass basis of band antireflection film)
(1) TiO
xN
yThe composition of layer
TiO for the glass basis of the band antireflection film of the example 4～14 of above-mentioned gained
xN
yLayer is by the nitrogen amount of ESCA mensuration with respect to titanium.In addition, the value of x and y is recorded by above-mentioned prerequisite.In the table, will be designated as N/Ti (at%) with respect to the nitrogen amount of titanium.
In addition, for example 4～7, on glass basis, only forming TiO
xN
yThe sample of layer is measured.Only form TiO even think
xN
yThe structure of layer, with respect to the nitrogen amount of titanium also with the matrix of band antireflection film in situation about measuring do not change.
[table 3]
(2) optical characteristics
The glass basis of the band antireflection film of the example 1～15 of above-mentioned gained and the VFL of example 16 are tried to achieve each following optical characteristics.In addition, the value of the result of the optical characteristics of example 1～7 for trying to achieve by simulation by the thickness and the refractive index of VFL and each layer.The results are shown in table 4.
(i) reflectivity of antireflection film (Rv)
Use visible reflectance Rv as reflectivity, the value that is reflected by the antireflection face for light from the incident of antireflection face side.That is, only obtain and to be the reflectivity of antireflection film.As benchmark, light source is the D65 light source with JIS R3106, and incident angle is 60 °.
In addition, for example 16, try to achieve the reflectivity of thermal treatment VFL afterwards
(ii transmissivity (Tv))
Use visual sense transmissivity Tv as transmissivity.As benchmark, light source is the A light source with JIS R 3106, and incident angle is 0 °.
(iii) tone (reflected colour)
As tone use value from the glass side (x, y).Light source is the D65 light source, and incident angle is 60 °.
(3) film resistance value
For the glass basis of the band antireflection film after the thermal treatment, use 2 probe resistance meters (Ha イ レ ス タ IP, Mitsubishi's oiling corporate system), measure the film resistance value of antireflection film.In example 16, with above-mentioned same, the VFL after the mensuration thermal treatment.Show the result in table 4.
(4) crackle
For the glass basis of the band antireflection film after the thermal treatment, have or not by optical microscope visual inspection antireflection film crackle to occur.Show the result in table 4.
(5) bending of matrix
For the glass basis of the band antireflection film after the thermal treatment, use digital vernier caliper to measure the amount of recess of face as the warpage of inboard in the intersection of diagonal of glass basis.Show the result in table 4.
(6) abrasion performance
For the glass basis of the band antireflection film after the thermal treatment, use Taber machine, with rotation abrasion wheel friction face, the state that the film after the viewing test is peeled off.For the mist degree before and after the determination test that do not have film to peel off, try to achieve △ H% (mist degree before and after the test poor).Show the result in table 4.In addition, the condition of Tai Shi wear test is that change loading 2.45N * 500.The more for a short time abrasion performance that shows of mist degree is good more.Consider preferably below 5%, particularly preferably in below 3% from practicality.
[table 4]
| Rv(％) | Tv(％) | Tone (x, y) | The film resistance value | Crackle | Warpage (mm) | Abrasion performance (△ H%) | |
| Example 1 | 3.463 | 88.103 | (0.308，0.326) | ＞1TQ | Do not have | ||
| Example 2 | 3.116 | 88.272 | (0.306，0.321) | ＞1TΩ | Do not have | ||
| Example 3 | 3.535 | 87.548 | (0.305，0.324) | ＞1TΩ | Do not have | ||
| Example 4 | 3.352 | 86.858 | (0.306，0.325) | ＞1TΩ | Do not have | ||
| Example 5 | 3.404 | 87.458 | (0.310，0.329) | ＞1TΩ | Do not have | ||
| Example 6 | 3.324 | 88.284 | (0.307，0.325) | ＞1TΩ | Do not have |
| Example 7 | 3.485 | 88.361 | (0.310，0.328) | ＞1TΩ | Do not have | ||
| Example 8 | 3.342 | 86.589 | (0.309，0.326) | ＞1TQ | Do not have | 0.5 | ＜1.0 |
| Example 9 | 3.658 | 93.506 | (0.311，0.327) | ＞1TΩ | Do not have | 0.5 | ＜1.0 |
| Example 10 | 4.238 | 93.971 | (0.314，0.327) | ＞1TΩ | Do not have | 0.5 | 1.18 |
| Example 11 | 4.630 | 94.426 | (0.317，0.331) | ＞1TΩ | Do not have | 1.0 | 0.98 |
| Example 12 | 4.022 | 93.948 | (0.316，0.322) | ＞1TΩ | Do not have | 0.5 | 1.41 |
| Example 13 | 3.925 | 94.064 | (0.314，0.322) | ＞1TΩ | Do not have | 1.0 | 6.23 |
| Example 14 | 4.328 | 87.695 | (0.310，0.330) | ＞1TΩ | Do not have | 0.5 | |
| Example 15 | 3.363 | 88.136 | (0.305，0.323) | ＞1TΩ | Have | ||
| Example 16 | 9.232 | 85.746 | (0.308，0.330) | ＞1TΩ |
As shown in Table 4, the glass basis of band antireflection film of the present invention (example 1～14) shows high resistance, and crackle do not occur because of thermal treatment.In addition, optical characteristics is antiradar reflectivity and high-transmission rate, and tone and the glass basis itself that does not form antireflection film are about equally.
Relative therewith, the tunicle that is formed by high-index material is and has occurred the crackle that caused by thermal treatment under the situation of individual layer (example 15) of titanium oxide layer.
The possibility of utilizing on the industry
If the transparent base as the matrix with antireflection film of the present invention uses glass plate, for being carried out, bending glass sheet processing glass plate is heated to 630～700 ℃ heat treatment even then can obtain, crackle, non-staining effect do not appear in antireflection film yet yet. In addition, in order to strengthen processing glass sheets glass plate is also obtained same effect when heating for 550～700 ℃.
Matrix with antireflection film of the present invention, as the low-reflection glass that the air regulator of automobile is used with glass, perhaps useful as the antiradar reflectivity glass that industry for building, various is used.
In addition, at this instructions of Japanese patent application 2005-023769 number quoting application on January 31st, 2005, the full content of claim and summary is as the disclosure of instructions of the present invention.
Claims (11)
1. be with the matrix of antireflection film, it is to have transparent base, and will by refractive index the formed tunicle of the high-index material more than 1.90 and by refractive index the formed tunicle of the low-index material below 1.56 from above-mentioned transparent base side begin according to this sequential cascade even level and the matrix of band antireflection film of antireflection film, it is characterized in that at least 1 layer of the tunicle that is formed by above-mentioned high-index material is the monofilm (a) of titanium oxynitrides layer, contain the stacked film (b) of titanium oxide layer and zirconia layer or contain the stacked film (c) of titanium oxynitrides layer and zirconia layer.
2. be with the matrix of antireflection film, it is to have transparent base, and will by refractive index the formed tunicle of the high-index material more than 1.90 and by refractive index the formed tunicle of the low-index material below 1.56 from above-mentioned transparent base side begin according to this sequential cascade even level and the matrix of band antireflection film of antireflection film, it is characterized in that at least 1 layer of the tunicle that is formed by above-mentioned high-index material is the monofilm (a) of titanium oxynitrides layer, the stacked film (c1) of the stacked film of titanium oxide layer and zirconia layer (b1) or titanium oxynitrides layer and zirconia layer.
3. the matrix of band antireflection film as claimed in claim 2 is characterized in that, at least 1 layer of the tunicle that is formed by above-mentioned high-index material is the stacked film (c1) of titanium oxynitrides layer and zirconia layer.
4. be with the matrix of antireflection film, it is to have transparent base, and will by refractive index the formed tunicle of the high-index material more than 1.90 and by refractive index the formed tunicle of the low-index material below 1.56 from above-mentioned transparent base side begin according to 4 layers of this sequential cascades the matrix of band antireflection film of antireflection film, it is characterized in that above-mentioned antireflection film is to begin to be laminated with in order the tunicle that is formed in the high-index material more than 1.90 by refractive index from the transparent base side, the monofilm of monox, the stacked film of titanium oxynitrides layer and zirconia layer (c1), the antireflection film of the monofilm of monox.
5. the matrix of band antireflection film as claimed in claim 4 is characterized in that, the tunicle that is formed in the high-index material more than 1.90 by above-mentioned refractive index is the monofilm of titanium oxide layer.
6. as the matrix of each described band antireflection film in the claim 1～5, it is characterized in that, with incident angle 60.Pressed the albedometer of visible light by the reflection of above-mentioned antireflection face below 6% from the light of above-mentioned antireflection film side incident.
7. as the matrix of each described band antireflection film in the claim 1,2,4, it is characterized in that the nitrogen amount with respect to titanium in the above-mentioned titanium oxynitrides layer is 0.1～80at%.
8. as the matrix of each described band antireflection film in the claim 1,2,4, it is characterized in that the nitrogen amount with respect to titanium in the preceding above-mentioned titanium oxynitrides layer of thermal treatment is 2～40at%.
9. as the matrix of each described band antireflection film in the claim 1,2,4, it is characterized in that, after the thermal treatment in the above-mentioned titanium oxynitrides layer nitrogen amount with respect to titanium be 0.1～20at%.
10. the matrix of band antireflection film as claimed in claim 1 or 2 is characterized in that, the total sum of the tunicle that is formed by high-index material and the tunicle that is formed by low-index material is more than 4 layers.
11. the job operation of the matrix of band antireflection film, it is characterized in that, have the matrix of each described band antireflection film in the claim 1～10 is sent into the heating process that is heated to the bending forming temperature in the heating furnace, and bending forming is the operation of desirable shape.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP023769/2005 | 2005-01-31 | ||
| JP2005023769 | 2005-01-31 | ||
| PCT/JP2006/301471 WO2006080502A1 (en) | 2005-01-31 | 2006-01-30 | Substrate with antireflection coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101111783A CN101111783A (en) | 2008-01-23 |
| CN101111783B true CN101111783B (en) | 2010-12-08 |
Family
ID=36740519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800033827A Expired - Fee Related CN101111783B (en) | 2005-01-31 | 2006-01-30 | Substrate with antireflection coating |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20070279750A1 (en) |
| EP (1) | EP1845392A4 (en) |
| JP (1) | JP5262110B2 (en) |
| CN (1) | CN101111783B (en) |
| WO (1) | WO2006080502A1 (en) |
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| US7692855B2 (en) * | 2006-06-28 | 2010-04-06 | Essilor International Compagnie Generale D'optique | Optical article having a temperature-resistant anti-reflection coating with optimized thickness ratio of low index and high index layers |
| JP2008201633A (en) * | 2007-02-21 | 2008-09-04 | Asahi Glass Co Ltd | Glass sheet with antireflection film and laminated glass for window |
| CN101393276B (en) * | 2007-09-21 | 2010-06-16 | 鸿富锦精密工业（深圳）有限公司 | Wide-band antireflective film and optical element with the wide-band antireflective film |
| KR20100135837A (en) * | 2008-04-24 | 2010-12-27 | 아사히 가라스 가부시키가이샤 | Low reflection glass and protective plate for display |
| JP2010231172A (en) * | 2009-03-04 | 2010-10-14 | Seiko Epson Corp | Optical article and method for producing the same |
| JP2010231171A (en) * | 2009-03-04 | 2010-10-14 | Seiko Epson Corp | Optical article and method for producing the same |
| JP5588135B2 (en) * | 2009-08-10 | 2014-09-10 | ホーヤ レンズ マニュファクチャリング フィリピン インク | Method for manufacturing optical article |
| JP5477084B2 (en) * | 2010-03-17 | 2014-04-23 | 豊田合成株式会社 | Semiconductor light emitting device and method for manufacturing the same, lamp, electronic device, mechanical device |
| JP2012032690A (en) * | 2010-08-02 | 2012-02-16 | Seiko Epson Corp | Optical article and manufacturing method thereof |
| JP2012128135A (en) * | 2010-12-15 | 2012-07-05 | Seiko Epson Corp | Optical article and method for manufacturing the same |
| TWI457615B (en) * | 2011-04-25 | 2014-10-21 | E Ink Holdings Inc | Color filter, optical grating structure and display module |
| WO2015093322A1 (en) * | 2013-12-16 | 2015-06-25 | 旭硝子株式会社 | Glass with anti-reflection film and method for manufacturing same |
| JP2017105643A (en) | 2014-04-24 | 2017-06-15 | 旭硝子株式会社 | Glass substrate with coating film and method for production thereof |
| WO2016010009A1 (en) * | 2014-07-16 | 2016-01-21 | 旭硝子株式会社 | Cover glass |
| CN105047080A (en) * | 2015-08-14 | 2015-11-11 | 河南镀邦光电股份有限公司 | Reflection-eliminating and anti-dazzle panel of display screen |
| JP6657872B2 (en) | 2015-12-03 | 2020-03-04 | Ａｇｃ株式会社 | Glass plate with anti-reflective coating |
| CN105549257A (en) * | 2015-12-28 | 2016-05-04 | 信利半导体有限公司 | Color filter substrate and making method thereof |
| EP3242150B1 (en) * | 2016-05-04 | 2019-01-02 | Essilor International | Optical article comprising an antireflective coating with a high reflection in the near infrared region (nir) |
| WO2019151321A1 (en) * | 2018-01-31 | 2019-08-08 | Ａｇｃ株式会社 | Antireflection film-equipped glass substrate and optical component |
| CN108642447A (en) * | 2018-05-08 | 2018-10-12 | 北京汉能光伏投资有限公司 | A kind of curved surface film-coated plate and preparation method thereof and include its solar components |
| WO2021070117A1 (en) * | 2019-10-08 | 2021-04-15 | Guardian Glass, LLC | Low-e matchable coated articles having absorber film and corresponding methods |
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| US5105310A (en) * | 1990-10-11 | 1992-04-14 | Viratec Thin Films, Inc. | Dc reactively sputtered antireflection coatings |
| JPH07119845B2 (en) * | 1990-11-27 | 1995-12-20 | ホーヤ株式会社 | Optical components |
| JPH0553002A (en) * | 1991-08-22 | 1993-03-05 | Canon Inc | Production of multilayered film by low-temperature vacuum vapor deposition and apparatus for production thereof |
| JP3039721B2 (en) * | 1992-03-24 | 2000-05-08 | キヤノン株式会社 | Vapor deposition material and method for producing optical thin film using the vapor deposition material |
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| JP2005250124A (en) * | 2004-03-04 | 2005-09-15 | Asahi Glass Co Ltd | Transmission type screen |
| EP1923362B1 (en) * | 2005-08-16 | 2015-09-16 | Asahi Glass Company, Limited | Infrared reflective glass plate and laminated glass for vehicle window |
| WO2007020791A1 (en) * | 2005-08-16 | 2007-02-22 | Asahi Glass Company, Limited | Laminated glass for vehicle window |
-
2006
- 2006-01-30 CN CN2006800033827A patent/CN101111783B/en not_active Expired - Fee Related
- 2006-01-30 EP EP06712614A patent/EP1845392A4/en not_active Withdrawn
- 2006-01-30 JP JP2007500632A patent/JP5262110B2/en not_active Expired - Fee Related
- 2006-01-30 WO PCT/JP2006/301471 patent/WO2006080502A1/en active Application Filing
-
2007
- 2007-07-31 US US11/830,999 patent/US20070279750A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JP5262110B2 (en) | 2013-08-14 |
| CN101111783A (en) | 2008-01-23 |
| EP1845392A1 (en) | 2007-10-17 |
| US20070279750A1 (en) | 2007-12-06 |
| WO2006080502A1 (en) | 2006-08-03 |
| JPWO2006080502A1 (en) | 2008-06-19 |
| EP1845392A4 (en) | 2009-06-03 |
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